Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/18—One oxygen or sulfur atom
  • C07D231/20—One oxygen atom attached in position 3 or 5
  • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
  • C07D231/24—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms having sulfone or sulfonic acid radicals in the molecule
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D411/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

• the present invention relates to new pyrazolyl-benzoyl derivatives with herbicidal activity, processes for the preparation of the pyrazolyl-benzoyl derivatives, compositions which contain them and the use of these derivatives or compositions containing them for weed control.
• Herbicidal pyrazolyl-benzoyl derivatives are known from the literature, for example from EP 352543.
• the task was to find new pyrazolyl-benzoyl derivatives with improved properties.
• L, M is hydrogen, -CC 6 alkyl, C -C 6 alkenyl, C -C 6 alkynyl,
• Z is a 5- or 6-membered heterocyclic, saturated or unsaturated radical containing one to three heteroatoms, selected from the group consisting of oxygen, sulfur or nitrogen, which may be replaced by halogen, cyano, nitro, a group -CO-R 8 , C ⁇ -C 4 -alkyl, C haloalkyl, C 3 -C 8 cycloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C4-haloalkylthio, di -C-C 4 -alkylamino, optionally substituted by halogen, cyano, nitro, C ⁇ -C-alkyl or C ⁇ -C 4 -haiogenalkyl-substituted phenyl or an oxo group, which may also be present in the tautomeric form as a hydroxyl group can, is substituted or with an andened, optionally by halogen,
• R B C 1 -C alkyl, -C-C 4 haloalkyl, -C -C alkoxy, or NR 9 Ri °
• R 9 is hydrogen or -CC alkyl
• Q is a pyrazole ring of the formula II linked in position 4
• R 2 represents hydrogen f, C ⁇ -C 4 alkyl or C 1 -C 4 haloalkyl and R 3 hydrogen f, C 1 -C 4 alkylsulfonyl, phenylsulfonyl or alkyl phenylsulfonyl,
• T halogen and L, M and Z have the meaning given above.
• the reactants and the auxiliary base are expediently used in approximately equimolar amounts. A small excess of the auxiliary base, for example 1.2 to 1.5 molar equivalents, based on II, may be advantageous.
• Suitable auxiliary bases are e.g. tertiary alkyl amines, pyridine or alkali carbonates, while methylene chloride is the solvent,
• reaction mixture is advantageously cooled to 0 -10 ° C, then at a higher temperature, e.g. stirred at a temperature of 25-50 ° C until the reaction is complete.
• the processing takes place in the usual way, e.g. the reaction mixture is poured into water and extracted with methylene chloride. After the organic phase has dried and the solvent has been removed, the crude 5-hydroxypyrazole ester can be used for the rearrangement without further purification.
• Preparation examples for benzoic acid esters of 5-hydroxy-pyrazoles can be found, for. B. in EP-A-282 944 or US 4,643,757.
• the rearrangement of the 5-hydroxypyrazole esters to the compounds of the formula Ic is advantageously carried out at from 20 ° C. to 40 ° C. in a solvent and in the presence of an auxiliary base and using a cyano compound as a catalyst.
• solvents which can be used are acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate or toluene.
• the preferred solvent is acetonitrile.
• Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali carbonates, which are used in an equimolar amount or up to a fourfold excess.
• the preferred auxiliary base is triethylamine in double amount.
• Suitable catalysts are cyanide compounds such as potassium cyanide or acetone cyanohydrin, for example in an amount of 1 to 50, in particular 5-20 mol percent, based on the 5-hydroxy-pyrazole ester.
• Acetone cyanohydrin is preferably added, for example, in amounts of 10 mole percent.
• the processing takes place in the usual way, e.g. the reaction mixture is acidified with dilute mineral acids such as 5% hydrochloric acid or sulfuric acid and extracted e.g. with methylene chloride or ethyl acetate.
• the extract is extracted with cold 5-10% alkali carbonate solution, the end product passing into the aqueous phase.
• the product of the formula Ic is precipitated by acidifying the aqueous solution, or extracted again with methylene chloride, dried and then freed from the solvent.
• 5-hydroxypyrazoles of the formula II used as starting material are known and can be prepared by processes known per se (cf. EP-A 240 001 and J. Prakt. Chem. 315, 382 (1973)). 1,3-Dimethyl-5-hydroxypyrazole is a commercially available compound.
• Benzoic acid derivatives of the formula III can be prepared as follows:
• the aryl halogen compounds or Arylsulfor.ate IV can be prepared in a manner known per se using heteroaryl stannates (Stille couplings), heteroaryl boron compounds (Suzuki couplings) or heteroaryl zinc compounds (Negishi reaction) V (see, for example, Synthesis 1987, 51-53, Synthesis 1992, 413) in the presence of a palladium or nickel transition metal catalyst and, if appropriate, a base to give the new compounds of the general formula III.
• benzoic acid derivatives of the formula III can also be obtained by appropriate bromine or iodine-substituted compounds of the formula VI
• L and M have the abovementioned meaning, in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.
• T, L, M and Z have the following meaning:
• -C-C 4 haloalkylthio Cj . -C 4 alkylsuflonyl, halogen, nitro or cyano M C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C ⁇ -C alkoxy, C ⁇ -C 4 alkylthio, C : -C 4 haloalkyl, C ⁇ -C 4 haloalkoxy,
• T chlorine, OH or C ⁇ ⁇ C alkoxy L M C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 -haloalkyl, C ⁇ -C 4 haloalkoxy, C ⁇ -C 4 haloalkylthio, C! -C 4 alkylsulfonyl, halogen, nitro or cyano Z as indicated above.
• the catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (0Ac) 2 , cyanides etc. in the known valence levels available.
• halogen compounds for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (0Ac) 2 , cyanides etc. in the known valence levels available.
• metal complexes with tertiary phosphines metal alkyl carbonyls, metal carbonyls, for example C0 (C0) 8 / Ni (CO) 4
• metal carbonyl complexes with tertiary phosphines for example (PPh 3 ) 2 Ni (CO)
• complexes complexed with tertiary phosphines gear metal salts are present.
• the latter embodiment is particularly preferred in the case of palladium as a catalyst.
• phosphine ligand The type of phosphine ligand is widely variable. For example, they can be represented by the following formulas:
• n is the numbers 1, 2, 3 or 4 and the radicals R 11 to
• R 14 for low molecular weight alkyl for example Ci-Cg-alkyl, aryl,
• Ci-C 4 alkylaryl for example benzyl, phenethyl or aryloxy.
• Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, but the substituents only have to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as Ci-C 6 -alkyl radicals, for example methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen, such as Ci-C ß -alkoxy radicals.
• the phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, one starts from customary commercially available metal salts such as PdCl or Pd (OCOCH 3 ) 2 and adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC H 9 ) 3 , PCH 3 (C 6 H5) 2 , 1 , 2-bis (diphenylphosphino) ethane.
• PdCl or Pd (OCOCH 3 ) 2 adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC H 9 ) 3 , PCH 3 (C 6 H5) 2 , 1 , 2-bis (diphenylphosphino) ethane.
• the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 molar equivalents, particularly preferably 1 to 5 molar equivalents.
• the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material VI.
• the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI.
• the reactive Onpartner water can also serve as a solvent at the same time, ie the maximum amount is not critical.
• Suitable inert solvents for carboxylation reactions are customary solvents, such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted ide such as dimethylformamide, per-substituted ureas such as tetra-Ci-C 4- alkylureas or nitriles such as benzonitrile or acetonitrile.
• hydrocarbons for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted ide such as dimethylformamide, per-substituted
• one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
• Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or bromide released during the reaction.
• tertiary amines are like tert.
• Alkylamines for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetra-alkyl-substituted urea derivatives such as tetra-C 1 -C 4 -alkyl urea, for example Tetramethyl urea.
• the amount of base is not critical, usually 1 to 10, in particular 1 to 5, moles are used.
• the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality in order to save costs, to be able to use small reaction vessels and to give the reactants maximum contact guarantee.
• the carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
• the carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C. In the case of discontinuous operation, it is expedient to maintain a constant pressure carbon monoxide is continuously pressed onto the reaction mixture.
• aryl halogen compounds VI used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses.
• the aryl bromides VI can also be obtained by direct bromination of suitable starting compounds [cf. eg monthly Chem. 99, 815-822 (1968)].
• R 15 is hydrogen, -CC 4 alkyl, -C -C haloalkyl, C 3 -C 8 cycloalkyl, optionally subst. Phenyl or trimethylsilyl,
• R 16 is hydrogen, -CC -haloalkyl, C 3 -C 8 cycloalkyl or optionally subst. Phenyl.
• aryl methyl ketones IVa can be prepared in the presence of a palladium or nickel transition metal catalyst and optionally a base by processes known from the literature by reaction with vinyl alkyl ethers and subsequent hydrolysis [cf. e.g. Tetrahedron Lett. 32, 1753-1756 (1991)].
• the ethynylated aromatics IVb can be prepared in a manner known per se by reacting aryl halogen compounds or aryl sulfonates IV with substituted acetylenes in the presence of a palladium or nickel transition metal catalyst (for example Heterocycles, 24, 31-32 (1986)).
• a palladium or nickel transition metal catalyst for example Heterocycles, 24, 31-32 (1986)
• the benzoyl derivatives IV used as starting compounds are known [cf. e.g. Coll. Czech. Chem. Commn. 40, 3009-3019 (1975)] or can be easily prepared by a suitable combination of known syntheses.
• T is -C-alkoxy and L, M as defined above.
• Isophthalic acid derivatives ivf can be prepared from the aldehydes IVe by known processes [see. J. March Advanced Organic Chemistry 3rd ed., Pp. 629ff, Wiley-Interscience Publication (1985)].
• the oximes IVg are advantageously obtained by reacting aldehydes IVe with hydroxylamine in a manner known per se [see. J. March Advanced Organic Chemistry 3rd ed., Pp. 805-806, Wiley-Interscience Publication (1985)].
• the conversion of the oxime IVg into nitrile IVh can also be carried out according to methods known per se [see. J. March Advanced Organic Chemistry 3rd ed., Pp. 931-932, Wiley-Interscience Publication (1985)].
• the aldehydes IVe required as starting compounds are known or can be prepared by known methods. For example, they can be synthesized from methyl compounds VII in accordance with Scheme 6.
• the residues T, M and L have the meaning given under Scheme 5.
• the methyl compounds VII can be reacted to the benzyl bromides VIII by generally known methods, for example with N-bromosuccinimide or 1,3-dibromo-5, 5-dimethylhydantoin.
• the conversion of benzyl bromides to benzaldehydes IVe is also known from the literature [cf. Synth. Commun. 22 1967-1971 (1992)].
• the precursors IVa to IVh are suitable for building up heterocyclic intermediates III.
• the acetylenes IVb and the alkenes IVe are suitable for the synthesis of 4-isoxazolyl, 5-isoxazolyl, 4, 5-dihydroisoxazol-4-yl, 4,5-di-hydroisoxazol-5-yl derivatives [cf. e.g. Houben-Weyl, Methods of Organic Chemistry, 4th ed., Vol. X / 3, pp. 843ff (1965)].
• 2-oxazolyl, 1,2, 4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl derivatives can be obtained, for example, by processes known from the literature [ see. e.g. J. Heterocyclic, former, 28, 17-28 (1991)] or 2-pyrrolyl derivatives [cf. e.g. Heterocycles 26, 3141-3151 (1987)].
• 1, 2, 4-triazol-3-yl derivatives are derived from benzonitriles IVh using known methods [cf. eg J. Chem. Soc. Determine 3461-3464 (1954)] ⁇ forth.
• 2-oxazolyl, 1, 2, 4-oxadiazol-5-yl, 1, 3, 4-oxadiazol-2-yl derivatives can be obtained from the benzoic acids IVf or the acid chlorides IVi obtained therefrom by standard processes, see. eg J. Heterocyclic Chem., 28, 17-28 (1991)] or 2-pyrrolyl derivatives [cf. eg heterocycles 26, 3141-3151 (1987)].
• 1, 2, 4-triazol-3-yl derivatives are from benzonitriles IVh according to known methods [cf. e.g. J. Chem. Soc. 3461-3464 (1954)].
• Oximes IVg can be converted into 3-isoxazolyl derivatives in a manner known per se via the intermediate stage of the hydroxamic acid chlorides IVk [cf. e.g. Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Vol. X / 3, pp. 843ff (1965)].
• -CC 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl,
• C -C 6 alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl -2-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-4-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl- 2-propenyl, 1,2-dimethyl
• C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l-methyl- 2-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3 pentynyl, l-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl,
• C ⁇ ⁇ C alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy,
• C ⁇ C 3 alkoxy such as methoxy, ethoxy, i-propoxy
• halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or -C ⁇ alkoxy as mentioned above.
• the above-defined group - (Y) n -S (0) m R 7 is, for example ⁇ C ⁇ -C 4 alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio, especially methylthio;
• C ⁇ -C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1, 1-dimethylethylsulfinyl, especially methylsulfinyl;
• C ⁇ -C 4 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1, 1-dimethylethylsulfonyl, especially methylsulfonyl;
• C ⁇ -C 4 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methyl-propoxysulfonyl, 2-methylpropoxysulfonyl and 1, 1-dimethylethoxysulfonyl, especially methoxysulfonyl;
• N-C ⁇ -C 4 alkylsulfamoyl such as N-methylsulfaoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl Dimethylethylsulfamoyl, especially N-methylsulfamoyl;
• N-C ⁇ -C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethylsulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butyl sulfinamoyl, N-1-methylpropylsulfinamoylpoyl, N-2 , 1-dimethylethylsulfinamoyl, especially N-methy1su1finamoyl;
• Di-C ⁇ -C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl , 1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-Nl, 1-dimethylethylsulfamoyl; especially dimethylsulfamoyl;
• Di-C ⁇ -C -Alkylsulfinamoyl as Dimethylsulfinamoyl, Diethylsulfina ⁇ Moyles, Dipropylsulfinamoyl, Dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methyl ethylsulfinamoyl, N- Methyl-N-1, 1-dimethylethylsulfinamoyl, di-1-methylethylsulfinamoyl, N-ethyl-Nl-methylethylsulfinamoyl and N-ethyl-Nl, 1-dimethylethylsulfinamoyl; especially Di e-thy1su1finamoyl, C ⁇ -C 4 alkyls
• C ⁇ -C-Alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1, 1-dimethylethylsulfonyloxy, especially
• C ⁇ -C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylsulfonamino, especially methylamines;
• C ⁇ -C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylamino-1-fonylamino;
• N-C ⁇ -C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinyl-N-methyl-amino, N-1 -Methylethylsulfinyl-N-methyl-amino, Nn-butylsulfinyl-N-methyl-amino, Nl-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and Nl, 1-dimethylethyl-sulfinyl -N-methylamino, especially N-methylsulfinyl-N-methylamino;
• N-C ⁇ -C 4 alkylsulfinyl-N-ethyl-amino such as N-methylsulfinyl-N-ethyl-amino, N-ethylsulfinyl-N-ethyl-amino, Nn-propylsulfinyl-N-ethyl-amino, N-1-methylethylsulfinyl -N-ethyl-amino, Nn-butylsulfinyl-N-ethyl-amino, N-1-methylpropylsulfinyl-N-ethyl-amino, N-2-methylpropylsulfinyl-N-ethyl-amino and Nl, 1-dimethylethylsulfinyl-N -ethyl-amino, especially N-methylsulfinyl-N-ethyl-amino;
• N-C ⁇ -C-alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfonyl-N-methyl-amino, Nn-propylsulfonyl-N-methyl-amino, N-1- Methylethylsulfonyl-N-methyl-amino, Nn-butylsulfonyl-N-methyl-amino, Nl-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and Nl, 1-dimethylethylsulfonyl- N-methylamino, especially N-methylsulfonyl-N-methylamino; N-C ⁇ -C 4 alkylsulfonyl-N-ethyl-amino such as N-methylsulf
• C ⁇ ⁇ C 4 -haloalkylthio such as chloromethylthio, dichloroethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2, 2-trifluorothio, 2-difluoroethyl, Chloro-2, 2-difluoroethylthio, 2,2-dichloro-2 fluoroethylthio, 2,2, 2-trichloroethylthio and pentafluoroethylthio, especially trifluoromethylthio.
• the group - (Y) n -CO-R 8 defined above stands for, for example
• C ⁇ -C 4 alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropyl carbonyl, 2-methylpropylcarbonyl and 1, 1-dimethylethylcarbor.y, especially methylcarbonyl;
• -CC alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-? Rop-oxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, l-methyl-propoxycarbonyl, 2-methylpropoxycarbonyl and 1, 1-dimethylet.oxycarbonyl, especially methoxycarbonyl;
• N-C ⁇ -C-alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl, and Nl, 1-dim especially N-methylcarbamoyl;
• Di-C ⁇ -C alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbaroyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N-1, 1-dimethylethylcarbamoyl, di-1-methylethylcarbamoy, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-Nl, 1-dimethyethylcarbamoyl; especially dimethylcarbamoyl;
• C -C 4 -alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbor.y-loxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1, 1-dimethylethylcarbonyloxy, especially methylcarbonyloxy;
• C 1 -C 4 -alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino, n-butylcarbonylamino, 1-methylpropylcarbonylamino, 2-methylpro- pylcarbonylamino and 1, 1-dimethylethylcarbonylamino, especially methylcarbonylamino;
• N-C ⁇ -C 4 alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl-N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-N-methyl-amino, N-1 -Methylethylcarbonyl-N-methyl-amino, Nn-butylcarbonyl-N-methyl-amino, Nl-methylpropylcarbonyl-N-methyl-amino, N-2-methylpropylcarbonyl-N-methyl-amino and Nl, 1-dimethylethylcarbonyl -N-methyl-amino, especially N-methylcarbonyl-N-methyl-amino.
• heteroaromatics such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3, 5-triazin-2-yl , 1, 2, 4-triazin-5-yl and 1,2, 4-triazin-3-yl, 1,2, -triazin-6-yl, 1,2,4, 5-tetrazin-3-yl;
• 5- to 6-membered, saturated or partially unsaturated heterocycles containing one to three nitrogen atoms and / or one or two oxygen or sulfur atoms such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrotienyl, tetrahydrothiopyran -2-yl, tetrahydrothiopyran-3 -yl, tetrahydrothiopyran-4-yl, 1, 3-dithiolan-2-yl, 1, 3-dithiolan-4 -yl, l-3-dithian-2-yl, 1, 3 Dithian-4-yl, 5,6-dihydro-4H-1,3-thiazin-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl,
• Halogen as mentioned above, in particular fluorine or chlorine,
• a group -COR 8 for example alkylcarbonyl as mentioned above, alkoxycarbonyl as mentioned above, N-alkylcarbamoyl as mentioned above, dialkylcarbamoyl as mentioned above; -CC alkyl as mentioned above,
• haloalkyl such as chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl,
• C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, especially cyclopropyl and cyclohexyl;
• C 1 -C 4 haloalkoxy such as chloroethoxy, dichloroethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1, 1,2 , 2-tetrafluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-l, 1, 2-trifluoroethoxy and pentafluoroethoxy, in particular C 3 -C 3 -haloalkoxy such as 2,2,2-trifluoroethyloxy and 2-chlorine -2,2-difluoroethoxy;
• Di-C ⁇ -C 4 alkylamino such as dimethylamino, diethyi- amino, dipropylamino, dibutylamino, N-methyl-N-ethylamino, N-methyl-N-propylamino, N-methyl-N-1-methylethylamino, N-methyl- N-1, 1-dimethylethylamino, di-1-methylethylamino, N-ethyl-N-1-methylethylamino and N-ethyl-Nl, 1-dimethylethylamino;
• an oxo group which may also be present in the tautomeric form as a hydroxyl group, is substituted, for example thiazolin-4, -dion-2-yl, 3-oxo-3H-1,2, -dithiazolyl or 2-oxo -2H-1,3,4-dithiazolyl.
• Benzo-fused 5- or 6-membered heteroaromatic rings are ⁇ example as benzofuranyl, benzothienyl, indolyl, benzoxazolyl, benz- isoxazolyl, benzothiazolyl, benzisothiazolyl, benzpyrazolyl, indazolyl, 1,2, 3-benzothiadiazolyl, 2, 1, 3-benzothiadiazolyl, benzotriazolyl , Benzofuroxanyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl or phthalazinyl. - games for particularly preferred connections of the general. Formula I are summarized in Table 1 below.
• the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
• the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.
• the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
• the following crops come into consideration, for example:
• the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
• the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
• the compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Atomizing, dusting, scattering or pouring can be used.
• the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. B.
• Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
• wetting agents adhesives, dispersants or emulsifiers.
• concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
• alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. B. lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylpheny
• Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
• Granules e.g. B. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid inert substances.
• Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, Kalk ⁇ stone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, Calciu - and magnesium sulfate, magnesium oxide, ground synthetic ⁇ materials, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
• Formulations generally contain from 0.001 to 98 wt -., Before ⁇ preferably 0.01 to 95 wt -.%, Of active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
• the compounds I according to the invention can be formulated, for example, as follows:
• I 20 parts by weight of compound no. 1.28 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
• aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
• Dissolved mixture which consists of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL. A stable emulsion concentrate is obtained.
• the pyrazolylbenzoyl derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
• diazines, 4H-3, 1-benzoxazine derivatives, benzothiadiazinones, 2, 6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, urides, ureas, diphenyl ethers, triazinones, uracils, benzofurane 1 derivatives, cyclohexane come as mixing partners , 3-dione derivatives in the 2-position z.
• Non-phytotoxic oils and oil concentrates can also be added.
• the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as), depending on the control target, the season, the target plants and the growth stage.
• Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
• the seeds of the test plants were sown separately according to species.
• the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
• the vessels were sprinkled lightly to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
• test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then are they treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants are either sown directly and grown in the same containers or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
• the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
• reaction mixture is filtered through a layer of silica gel, with methyl tert. -butyl ether washed and concentrated. The residue is chromatographed on silica gel using toluene / ethyl acetate as the eluent.
• dilute hydrochloric acid is first added and methyl tert. -butyl ether extracted.
• the ether phase is then extracted with 5% potassium carbonate solution.
• the product is extracted with ethyl acetate from the aqueous phase.
• the ethyl acetate phase is dried with sodium sulfate and concentrated. 1.2 g of crude product are obtained, which is purified by column chromatography.

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